Addition products of acrylonitrile and drying oil acids and esters



Patented Apr. 20, 1948 ADDITION PRODUCTS OF ACRYLONITRILE AND DRYING OILACIDS AND ESTERS Herman A. Bruson, Rydal, and Warren D. Niederhauser,Philadelphia, Pa., assignors to The Recinous Products & ChemicalCompany, Philadelphia, Pa., a corporation of Delaware No Drawing.Application June 21, 1945. Serial No. 800,850

'16 Claims. (Cl. 280-404) 1 *This invention relates to addition productsof aicrylonitrile and drying oil acids or their esters.

It has heretofore been proposed to polymerize acrylic acid derivativeswith drying oils. The products thus obtained are resinous copolymers 01'very large molecular weight.

In contrast thereto, the products of this invention are not polymers orresins but cyano-carboxylic acids or cyano-esters oi' definitecomposition, The products in general are oils or liquids which can bedistilled at low pressures except for the higher esters or esters ofpolyhydric alcohols of high molecular weight.

The products are useful in the form of esters as plasticizers. They arealso valuable intermediates for the preparation or dicarboxylic acidsupon hydrolysis and can be reduced to aminocarboxylic acids andaminoalcohols, derivatives which are of value in the manufacture oiplastics.

The products of this invention are obtained by reacting by addition atabout 80 C. to about 300 C. acrylonitrile and a long-chained fatty acid,or an ester thereof, in which there are present two oleiinic linkages inconjugate relationship. The addition is effected in the absence of anypolymerizing catalyst, and advantageously in the presence of aninhibitor for polymerization and/or under n inert atmosphere, forexample, nitrogen or arbon dioxide.

Typical fatty acids possessing at least two olenic linkages, of which apair is in conjugate elationship, are ti-elaeo-stearic acid,p-elaeostearic acid, a-licanic acid, p-licanic acid, and 9,11-octadecadienic acid. Technical mixtures of such acids resulting fromhydrolysis of tung oil or oiticica oil may be used. There may also beused the dehydration products of castor oil fatty acids or the acidscontaining conjugated double bonds formed by alkaline rearrangement ofvarious unsaturated fatty acids and esters.

In place of the free fatty acids, there may be reacted the esters formedfrom these acids and alcohols, both monohydric and polyhydric. Oneimportant class of esters is formed from such monohydric alcohols asmethyl, ethyl, isopropyl,

butyl, isobutyl, amyl, hexyl, octyl, dodecyl, cetyl,

cyclohexyl, benzyl, chloroethyl, phenoxyeth'yl. tert.-butylphenoxyethyl,tetrahydroiurfuryl, and the like. There may also be used the phenylesters. The esters of the lower alcohols yield cyanoesters which arereadily distiilable at reduced pressures. Some of the higher alcoholsyield waiw products. There may likewise be used esters oi polyhydricalcohols such as glycols, glycerine. pentaerythritol, sorbitol, etc.,and the conjugated 2 fatty acids. In the addition of acrylonitriie tothese rather complex esters, it is preferable to eflect the reaction inthe presence oi a small amount of an inhibitor such as hydroquinone,pyrosallol, naphthyiamine, a-naphthol, diphenylamine, or the like.

The following examples, illustrative oi the preparation of variousaddition products, present details of advantageous procedures which maybe used for the purposes of this invention. Parts indicated are byweight.

Example 1 A mixture of 107 parts of tung oil fatty acids and 48 parts ofacrylonitrile was heated under reflux at -l30 C. for forty-eight hours.The product was distilled to give 146 parts (73% yield) of additionproduct having a boiling range of 240255 C./3 mm., a refractive index, aof 1.4929, and a density, d4", 01' 0.9632. From analytical data(nitrogen, 4.61% and iodine number of 133, as compared to the calculatedvalues [or CmHnOaN of 4.23% nitrogen and 153.5 iodine number). it isevident that the primary product is that formed by addition oi one moioi. fatty acid and one moi of acrylonitrile.

Example 2 A mixture of 41.7 parts of p-elaeostearic acid, 10.6 parts ofacrylonitrile, and 0.2 part of hydroquinone was heated under reflux forfifteen hours, the temperature of the reaction mixture slowly risingfrom 90 to 150 C. The product was distilled to give 34 parts (69% yield)of pale-yellow oil having a boiling range 01' 255-265 C./5 mm., arefractive index, o of 1.4905, and a density, d4", 01 0.9774. Fromanalytical data (nitrogen, 4.05%; iodine number, 128; and acid number,160, as compared to the calculated values for CaHazOzN of: iodinenumber, 153.5; acid number, 1'10; and nitrogen, 4.23%), it is evidentthat the primary product is that formed by addition of one mol 0! fattyacid and one moi of acrylonitrile.

Example 3 A mixture oi 24 parts of p-licanlc acid, 12 parts ofacrylonitrile, and 0.2 part of hydroqulnone was heated under reflux forforty hours at 90- 112 C. The product was distilled to give 9.5 parts ofan addition product having a boiling range of 260-265 C./i mm., arelractive index. 12 ,25, 0! 1.5000.

Example! A mixture of 83.4 parts of octadecadlenic acid. prepared by thedehydration of castor oil fatty acids. 82 parts of acryionitrile, and0.2 part of pyrogalloi was heated in an autoclave for fourteen hours at180 C. The reaction mixture was distilled to give 28 parts of adduct,having a boiling range of 250-250 C./4 mm., a density. d9, of 0.9575,and a refractive index, n oi 1.48.

Example 5 Example 6 A mixture of 43.8 parts of methyl elaeostearate and13.2 parts of acrylonitriie was heated under reflux for twenty hours at90-180 C. The product was distilled to give 28.5 parts of light yellowoil, boiling at 225-230 C./2 1pm., having a refractive index, 11 of1.4833 and a density. 114. of 0.9507. The analytical data (nitrogen.3.87%. and iodine number, 125) show this distillate to be chiefly theaddition product of one moi of ester and one moi of acrylonitriie.

Ezample 7 A mixture of 34.5 parts of methyl iicanate, 15 parts ofacrylonitrile, and 0.1 part of hydroquinone was heated under reflux foriorty-flve hours at 85-95 C. Upon distillation, the product wascollected at 235-245 C./1 mm. It had a refractive index, n of 1.4927.From the nitrogen analysis of 3.57%. it appears that most of thedistillate is the addition product of one moi of ester and one ofacrylonitrile.

Example 8 A mixture of 88 parts of methyl octadccadienate, 24 parts ofacrylonitrile, and 0.2 part of hydroquinone was heated in an autoclavefor thirteen hours at 250 C. The product was distilled to give 38 partsof a light yellow oil boiling at 235-245 C./8 mm. and having a density,d4". of 0.9424 and a refractive index, n of 1.4757. From the analyticaldata (nitrogen, 3.76%, and iodine number, 84, as compared to thecalculated values for CraHaiOsN of 4.03% nitrogen and iodine number,73), it is evident that the distillate is chiefly the addition productof one moi of ester and one moi of acrylonitrile.

In place of the above methyl esters, there may be used any other ester,the product in each case being composed primarily of the adduct of onemoi of acryionitrile per unit of fatty acid in the ester. 0

Example 9 '4 heated and stirred under reflux at 115 C. for three hours.The product was acidified to Congo red with concentrated hydrochloricacid. washed with hot water, and the solvent removed on the steam bathunder reduced pressure to give 864 parts of crude isomeric dicarboxyiicacids. One of the isomers which was separated by recrystallization.first from nitroethane and then from hutanol, melted at 110 C.

We claim:

1. Monomeric products formed by the addition at C. to 300 C. ofequimolecuiar proportions of (a) acrylonitrile and (b) a compound fromthe class consisting of drying oii fatty acids having coniugate oieflnicbonds and esters of said acids and alcohols having the alcoholichydroxyl group as the sole reactive functional group thereof.

2. Monomeric products formed by the addition at 80 C. to 300 C. ofequimolecular proportions of (a) acrylonitrile and (b) a drying oilfatty acid having conjugate oieflnic bonds.

3. Monomeric products formed by the addition at 80 C. to 300 C. ofequimolecular proportions of (a) acryionitrile and (b) esters of dryingoil fatty acids having conjugate oleilnic bonds and alcohclshaving thealcoholic hydroxyl group as the sole reactive functional group thereof.

4. Monomeric products formed by the addition at 80 C. to 300 C. ofequimoiecular proportions of (a) acryionitrile and (b) esters of dryingoil fatty acids having conjugate oleilnic bonds and saturated monohydricaliphatic alcohols of not over four carbon atoms.

5. Monomeric products formed by the addition at 80 C. to 300' C. ofequimoiecular proportions of (a) acryionitrile and (b) esters ofeiaeostearic acid and alcohols having the alcoholic hydroxyl group asthe sole reactive functional group thereof.

6. Monomeric products formed by the addition at 80 C. to 300' C. orequimoiecuiar proportions of (a) acryionitrile and (b) esters ofoctadecadienic acid and alcohols having the alcoholic hydroxyi group asthe sole reactive functional group thereof.

7. A monomeric product formed by addition at 80 C. to 800' C. ofequimolecuiar proportions of (a) acryionitrile and (0) methylelaeostearate.

8. A monomeric productformed by addition at 80 C. to 300' C. ofequimolecular proportions of (a). acrylonitriie and (b) methyloctadecadienate.

0. A monomeric product formed by addition at 80 C. to 300' C. ofequimoiecular proportions of (a) acryionitrile and (b) octadecadienicacid.

10. A method of preparing new monomeric products which comprisesreacting by addition between 80 C. and 300 C. equimolecuiar proportionsof acrylonitrile and of a compound from the class consisting of dryingoil fatty acids having conjugate oleflnic bonds and esters of said acidsand alcohols having the alcoholic hydroxyl gfoup as the sole reactivefunctional group there- 0 I 11. A method of preparing new monomericproducts which comprises reacting by addition between 80 C. and 300 C.in the presence of a polymerization inhibitor equimoiecular proportionsof acrylonitriie and a drying oil fatty acid having conjugate oleflnicbonds.

12. A method of preparing new monomeric products which comprisesreacting by addition between 8 C. and 800 C. in the presence of apolymerization inhibitor equimolecular proportions of acrylonitrile andof esters of drying oil fatty acids having conjugate olefinio bonds andsaturated monohydric aliphatic alcohols of not over {our carbon atoms.

13. A method of preparing new monomeric products which comprisesreacting by addition between 80 C. and 300 C. under an inert atmosphereequimolecular proportions of acryionitriie and of esters of drying oilfatty acids having conjugate oiefinic bonds and saturated monohydricaliphatic alcohols of not over four carbon atoms.

14. A method of preparing new monomeric products which comprisesreacting by addition between 80 C. and 300 C. under an inert atmosphereequirnolecular proportions of acrylonitrile and of esters ofelaeostearic acid and a saturated monohydric aliphatic alcohol of notover four carbon atoms.

15. A method of preparing new monomeric products which comprisesreacting by addition between 80 C. and 300 C. under an inert at-REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,217,632 Wolfe Oct. 8, 19402,375,937 Miller et a1 May 15, 1945 2,382,803 Miller et al Aug. 14, 1945Certificate of Correction Patent No. 2,440,14o.

April 20, 1948.

HERMAN A. BRUSON ET AL.

It is hereby certified that errors app numbered patent requiringcorrection as car in the printed specification of the above follows:Column 3, line 11, for 1.48 read 1.4858; column 4, line 74, claim 12,for 8 0. read U.; and that the said Letters Patent should be read withthese corrections the record of the case in the Patent Ofiice.

Signed and sealed this 20th day of July, A. D. 1948.

therein that the same may conform to THOMAS F. MURPHY,

Assistant Commissioner of Patents.

tions of acrylonitrile and of esters of drying oil fatty acids havingconjugate olefinio bonds and saturated monohydric aliphatic alcohols ofnot over {our carbon atoms.

13. A method of preparing new monomeric products which comprisesreacting by addition between 80 C. and 300 C. under an inert atmosphereequimolecular proportions of acryionitriie and of esters of drying oilfatty acids having conjugate oiefinic bonds and saturated monohydricaliphatic alcohols of not over four carbon atoms.

14. A method of preparing new monomeric products which comprisesreacting by addition between 80 C. and 300 C. under an inert atmosphereequirnolecular proportions of acrylonitrile and of esters ofelaeostearic acid and a saturated monohydric aliphatic alcohol of notover four carbon atoms.

15. A method of preparing new monomeric products which comprisesreacting by addition between 80 C. and 300 C. under an inert at-REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,217,632 Wolfe Oct. 8, 19402,375,937 Miller et a1 May 15, 1945 2,382,803 Miller et al Aug. 14, 1945Certificate of Correction Patent No. 2,440,14o.

April 20, 1948.

HERMAN A. BRUSON ET AL.

It is hereby certified that errors app numbered patent requiringcorrection as car in the printed specification of the above follows:Column 3, line 11, for 1.48 read 1.4858; column 4, line 74, claim 12,for 8 0. read U.; and that the said Letters Patent should be read withthese corrections the record of the case in the Patent Ofiice.

Signed and sealed this 20th day of July, A. D. 1948.

therein that the same may conform to THOMAS F. MURPHY,

Assistant Commissioner of Patents.

